BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link and their application in asymmetric catalysis

Article abstract of DOI:10.1016/j.tetasy.2012.06.019

New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements and a C₁ backbone symmetry have been prepared from (S_a)- and (R_a)-1,1′-binaphthyl-2, 2′-diol (BINOL) and (S)-N-benzyl-1-(pyr

Full text of DOI:10.1016/j.tetasy.2012.06.019

Tetrahedron: Asymmetry 23 (2012) 1052–1057
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
BINOL-derived diphosphoramidites bearing unsymmetrical 1,2-diamine link
and their application in asymmetric catalysis
Konstantin N. Gavrilov a, , Alexei A. Shiryaev a, Ilya V. Chuchelkin a, Sergey V. Zheglov a,
⇑
Eugenie A. Rastorguev b, Vadim A. Davankov b, Armin Börner c
a Department of Chemistry, Ryazan State University, 46 Svoboda Street, 390000 Ryazan, Russian Federation
b Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 119991 Moscow, Russian Federation
c Leibniz-Institut für Katalyse an der Universität Rostock e.V., A.-Einstein-Str. 29a, 18059 Rostock, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 May 2012
Accepted 26 June 2012
New P,P-bidentate diastereomeric diphosphoramidite chiral ligands with mixed stereogenic elements
and a C1 backbone symmetry have been prepared from (Sa)- and (Ra)-1,10-binaphthyl-2,20-diol (BINOL)
and (S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine and are fully characterized. The use of these ligands
provides up to 84% ee in the Pd-catalyzed asymmetric allylic substitution of (E)-1,3-diphenylallyl acetate
and up to 95% ee in the Rh-catalyzed asymmetric hydrogenation of a-dehydrocarboxylic acid esters. The
results indicate that the catalytic performance is highly affected by the axial chirality of the binaphthyl
moieties of the ligand and the nature of the solvent.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
modular structure enables the formation of extensive ligand li-
braries and easy fine-tuning for a specific catalytic reaction.15,16
The preparation of drugs, agrochemicals, pheromones, food
additives, fragrances, stereoindividual polymers and other fine
chemicals and natural compounds is based on modern approaches
to the synthesis of enantiomerically pure substances. One of the
leading approaches is asymmetric metal complex catalysis, be-
cause it can provide very high reactivity and stereoselectivity,
and is environmentally friendly. Indeed, the use of highly selective
catalytic systems is one of the basic principles of ‘green chemis-
try’.1–8 In turn, the successful development of transition metal cat-
alyzed asymmetric processes over the last few decades has been
largely steered by the introduction of new chiral ligands, among
which phosphorus-containing compounds are worth noting.6,9–12
Since the early 1970s, an impressive number of chiral phospho-
rus-based ligands have been applied in many asymmetric catalytic
reactions.1–13 Nevertheless, only a handful of them (so-called priv-
ileged ligands), rooted in a few core structures, can be regarded as
truly successful in demonstrating proficiency in various mechanis-
tically unrelated reactions.14 Among the phosphite-type chiral li-
It should be noted that much attention has been focused on P-
monodentate BINOL-based phosphoramidites.15–18 In contrast,
only a limited number of P,P-bidentate diphosphoramidites, in par-
ticular those derived from chiral diamines, have been reported to
date, despite their easy accessibility. Thus, a small series of C2-sym-
metric diphosphoramidites L1a–d (Fig. 1) has been successfully ap-
plied in the Rh-catalyzed enantioselective hydrogenation of (Z)-
methyl 2-acetamido-3-phenylacrylate and in the Cu-catalyzed
enantioselective conjugate addition of diethylzinc to 2-cyclohexe-
none with good enantioselectivities.16,19 Diastereomeric diphosph-
oramidites with C1 symmetry from D-(+)-xylose L2a,b (Fig. 2) have
been used productively in asymmetric Cu-catalyzed 1,4-addition
and allylic substitution reactions, and especially in Pd-catalyzed
allylic substitution processes.20–22
O
P
O
P
gands phosphoramidites, those with
a
BINOL-backbone
O
O
O
O
completely satisfy this definition.15 Phosphoramidites are highly
versatile, readily accessible and efficient stereoselectors. Their
=
(
)
n
O
N
N
O
Ph
Ph
L1a-d
⇑
Corresponding author. Tel.: +7 4912 280580; fax: +7 4912 281435.
E-mail addresses: k.gavrilov@rsu.edu.ru (K.N. Gavrilov), hagehoge@mail.ru (A.A.
Figure 1. The P,P-bidentate diphosphoramidites based on symmetrical chiral
Shiryaev), armin.boerner@catalysis.de (A. Börner).
diamines.
0957-4166/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetasy.2012.06.019

K. N. Gavrilov et al. / Tetrahedron: Asymmetry 23 (2012) 1052–1057
1053
3a (dP 148.6 and 146.4) and 3b (dP 150.4 and 145.3). Both ligands
are readily available and can be prepared on a gram scale. In fact,
(S)-N-benzyl-1-(pyrrolidin-2-yl)methanamine 1 can be easily syn-
thesized in three steps from inexpensive (S)-pyroglutamic acid.35
Furthermore, BINOL is commercially available in both enantio-
meric forms and is one of the least expensive chiral auxiliaries cur-
rently on the market. It should be noted that ligands 3a,b have in
their structures, the skeletons of two famous kinds of P-monoden-
tate BINOL-based phosphoramidites LA and LB (Fig. 3).15–18
O
SiMe3
O
P
O
O
HN
O
O
O
=
O
O
O
NH
SiMe3
P
a
b
(Sa)-, (Ra)-
L2a,b
O
Figure 2. The P,P-bidentate diphosphoramidites based on 3,5-dideoxy-3,5-dia-
mino-1,2-O-isopropylidene-ribofuranose as an unsymmetrical chiral diamine.
O
O
N
O
O
R1
N
O
O
R
P
=
P
O
Herein we report on the synthesis and characterization of novel
C1-symmetric P,P-bidentate diastereomeric BINOL-based diph-
osphoramidite ligands containing an unsymmetrical 1,2-diamine
core and on their evaluation in Pd-catalyzed asymmetric allyla-
tions and Rh-catalyzed asymmetric hydrogenations. It should be
noted that enantioselective Pd-catalyzed allylic substitution has
emerged as a powerful synthetic tool, which is tolerant of various
functional groups in the substrate and which operates with a wide
range of C-, N-, O-, S- and P-nucleophiles. As a result, Pd-catalyzed
allylic substitution is a novel and highly efficient strategy in the to-
tal synthesis of enantiopure natural and unnatural products.3,23–31
The enantioselective hydrogenation, using inexpensive molecular
hydrogen and a small amount of a catalyst, is one of the most ma-
ture and dependable types of catalytic asymmetric transforma-
tions, and this technology has become widely used in the
pharmaceutical and agrochemical industries.32,33 On the other
hand, both catalytic processes are common benchmark tests for
initial ligand screening. From a functional point of view, the enan-
tiomeric excesses obtained are the simplest indexes for evaluating
new chiral ligands.29,30,34
O
LA
LB
(Sa)- or (Ra)-
Figure 3. Two very efficient types of P-monodentate BINOL-based
phosphoramidite.
Compounds 3a,b readily reacted with [Pd(allyl)Cl]2 (CH2Cl2/
THF, AgBF4 as a chloride scavenger, room temperature, 3 h) to give
cationic metallochelates 4a,b of the type [Pd(allyl)(L)]BF4
(Scheme 2). Duplication of the AX systems in the 31P NMR spectra
(in CDCl3) of complexes 4a [dP 146.3,
d and dP 135.6, d,
2JP,P = 114.8 Hz (64%); dP 144.7,d and dP 135.1, d, JP,P = 119.8 Hz
2
2
(36%)] and 4b [dP 148.4, d and dP 133.4, d, JP,P = 118.3 Hz (72%);
dP 145.7, d and dP 133.2, d, JP,P = 123.1 Hz (28%)] indicated the
2
presence of their exo- and endo-isomers.36 The AX systems were
observed in the 31P NMR spectra of complexes 4a,b due to the pres-
ence of the two different phosphoramidite phosphorus atoms in
the coordination sphere of the palladium. The MALDI TOF/TOF
mass spectrometry and elemental analysis data (see Section 4)
were also in good agreement with the proposed structures of 4a,b.
2. Results and discussion
0.5 [Pd(allyl)Cl]2, AgBF4
- AgCl
P
BF4
Diastereomeric diphosphoramidite ligands 3a,b were synthe-
sized very efficiently from 1,2-diamine 1 via reaction with 2 equiv
of the appropriate enantiomer of phosphorylating reagent 2a or 2b
in toluene in the presence of Et3N as an HCl scavenger and DMAP
as a catalyst (Scheme 1). The new ligands were stable during puri-
fication on basic aluminum oxide and isolated in good yields as
white solids. They can also be stored in the solid form under dry
conditions at room temperature over several months without any
degradation. Diphosphoramidites 3a,b were fully characterized
by 1H, 13C, and 31P NMR spectroscopy, MALDI TOF/TOF mass spec-
trometry as well as by elemental analysis. The 31P, 1H, and 13C NMR
spectra were as expected for these C1 ligands. In particular, for each
compound two signals with equal intensity were observed in the
31P NMR spectrum. Two different phosphoramidite phosphorus
atoms displayed two distinct singlets in the 31P NMR spectrum of
Pd
L
P`
4a,b (L = 3a,b)
Scheme 2. Synthesis of cationic palladium complexes 4a,b.
Our initial studies on the application of new diastereomeric
diphosphoramidites 3a,b and their cationic palladium complexes
4a,b in catalysis focused on the Pd-catalyzed asymmetric allylic
substitution of racemic (E)-1,3-diphenylallyl acetate 5. We first
tested the new stereoselectors in the allylic sulfonylation of 5 with
p-TolSO2Na as the S-nucleophile, using standard conditions (Ta-
ble 1). The reaction proceeded smoothly to afford sulfone 6a in
good yields and with moderate to good enantioselectivity [up to
O
Cl
P
+ 2
O
N
O
O
O
2a,b
N
P
N
H
=
P
O
NH
5 Et3N, PhCH3
DMAP
O
O
O
O
1
- 2 Et3N·HCl
3a,b
a
b
(Sa)-, (Ra)-
Scheme 1. Synthesis of the diastereomeric diphosphoramidites 3a,b.

1054
K. N. Gavrilov et al. / Tetrahedron: Asymmetry 23 (2012) 1052–1057
82% ee for the (S)-enantiomer, Table 1, entry 6]. The L/Pd molar ra-
tio did not have a profound influence on the enantioselectivity. The
configuration of the BINOL-based phosphacycles determined the
absolute configuration of the desired sulfone: ligand 3a led to the
formation of (R)-6a, while ligand 3b led to the formation of (S)-
6a. It should be noted that diastereomer 3b is slightly more effi-
cient (Table 1, entries 1–3 and 4–6).
In order to further investigate the potential of the new readily
available diphosphoramidite ligands 3a,b, they were tested in
the Rh-catalyzed enantioselective hydrogenation of prochiral
methyl esters of unsaturated acids, dimethyl itaconate 7a and
(Z)-methyl 2-acetamido-3-phenylacrylate 7b (Table 2). In all
Table 2
Rh-catalyzed hydrogenation of
a
-dehydrocarboxylic acid esters 7a,ba
Table 1
a
Pd-catalyzed allylic sulfonylation and alkylation of (E)-1,3-diphenylallyl acetate 5
CO2Me
CO2Me
H2, cat
Nu
*
R2
OAc
Ph
R2
*
NuX, cat
Solvent
Solvent
R1
R1
Ph
Ph
Ph
8a,b
7a,b
5
6a,b
Nu = SO2pTol, X = Na, 6a
Nu = CH(CO2Me)2 X = H, 6b
R1 = H, R2 = CH2CO2Me, 7a and 8a
R1 = Ph, R2 = NHAc, 7b and 8b
Entry
Ligand
L/Pd
Solvent
Conversionb (%)
ee (%)
Entry
Ligand
Solvent
Conversion (%)
ee (%)
Allylic sulfonylation with sodium p-toluenesulfinatec
Hydrogenation of dimethyl itaconate 7ab
1
2
3
4
5
6
3a
3a
3a
3b
3b
3b
1
2
1
1
2
1
THF
THF
THF
THF
THF
THF
75
96
64
93
89
75
70 (R)
60 (R)
73 (R)d
77 (S)
75 (S)
82 (S)e
1
2
3
4
5
3a
3a
3b
3b
3b
CH2Cl2
CF3CH2OH
CH2Cl2
CH3OH
CF3CH2OH
0
100
0.4
24
—
94 (R)
3 (S)
2 (S)
95 (S)
100
Hydrogenation of (Z)-methyl 2-acetamido-3-phenylacrylate 7bc
6
7
8
9
10
11
Allylic alkylation with dimethyl malonate (BSA, KOAc)f
7
8
9
10
11
12
13
14
15
16
17
18
3a
3a
3a
3b
3b
3b
CH2Cl2
CH3OH
CF3CH2OH
CH2Cl2
CH3OH
0
30
93
19
97
—
3a
3a
3a
3a
3a
3a
3b
3b
3b
3b
3b
3b
1
2
1
2
1
1
1
2
1
2
1
1
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
THF
CH2Cl2
THF
100
98
37
38
95
44
20
18
32
29
98
94
62 (R)
59 (R)
57 (R)
65 (R)
65 (R)d
64 (R)d
17 (S)
13 (S)
49 (S)
65 (S)
17 (S)e
84 (S)e
16 (R)
71 (R)
95 (S)
66 (S)
93 (S)
CF3CH2OH
100
a
All reactions were carried out with 1 mol % [Rh(cod)2]BF4 at 25 °C, L/Rh = 1 and
1 bar H2 for 24 h.
b
The conversion of substrate 7a and enantiomeric excess of 8a were determined
by GC (Lipodex E, 25 m ꢀ 0.25 mm, 80 °C, 1 mL/min).
c
The conversion of substrate 7b and enantiomeric excess of 8b were determined
by GC (Lipodex E, 25 m ꢀ 0.25 mm, 145 °C, 1 mL/min).
a
All reactions were carried out with 2 mol % [Pd(allyl)Cl]2 at room temperature
for 48 h.
b
cases, the catalysts were generated in situ from the complex
[Rh(cod)2]BF4 (cod is 1,5-cyclooctadiene) and the corresponding
ligand in the appropriate solvent. Unfortunately, negligible con-
version and enantioselectivity were observed in the hydrogena-
tion of substrate 7a in CH2Cl2 or CH3OH (Table 2, entries 1, 3
and 4). In strong contrast, in a CF3CH2OH medium, both diaste-
reomeric ligands 3a and 3b provided quantitative conversion of
7a, and essentially equally very good levels of asymmetric induc-
tion (94% and 95% ee) with the (R)- and (S)-configuration of 8a,
respectively (Table 2, entries 2 and 5). The results achieved with
3a and substrate 7b show that the enantioselectictivity and con-
version increased in the consistent order: CH2Cl2 < CH3OH < CF3-
CH2OH and that product (R)-8b was formed with 71% ee
(Table 2, entries 6–8). At the same time, ligand 3b afforded 8b
with opposite absolute configuration but with superior enanti-
oselectivity [up to 95% ee for the (S)-enantiomer, Table 2, entry
9], probably due to the matched combination of the (2S)-stereo-
center of the 1,2-diamine core with the (Ra)-BINOL fragments.
High enantioselectivity was observed for both solvents CH2Cl2
and CF3CH2OH (95% and 93% ee, respectively), but quantitative
conversion of 7b, only for CF3CH2OH (Table 2, entries 9–11).
Isolated yield of 6a.
Enantiomeric excess of 6a was determined by HPLC [Daicel Chiralcel OD-H,
c
C6H14/i-PrOH = 4/1, 0.5 mL/min, 254 nm, t(R) = 16.3 min, t(S) = 18.5 min].
d
With complex 4a as the catalyst.
With complex 4b as the catalyst.
The conversion of substrate 5 and the enantiomeric excess of 6b were deter-
e
f
mined by HPLC [Daicel Chiralcel OD-H, C6H14/i-PrOH = 99/1, 0.3 mL/min, 254 nm,
t(R) = 28.0 min, t(S) = 29.3 min].
Next we turned our attention to the use of 3a,b and 4a,b in
the alkylation of 5 with dimethyl malonate as the C-nucleophile
(in THF and CH2Cl2) (Table 1), the enantiomeric excesses were
generally moderate to good with up to 65% (R) and 84% (S),
respectively. Similar to the Pd-catalyzed allylic sulfonylation,
the use of 3a afforded the reaction product 6b with an (R)-con-
figuration, while the use of 3b gave the (S)-configuration. Ligand
3a gave (R)-6b with modest enantiomeric purity (57–65% ee)
(Table 1, entries 7–12) regardless of the L/Pd molar ratio and
the nature of the solvent; the highest conversion was observed
in CH2Cl2. On the contrary, with ligand 3b (a diastereoisomer
of 3a with respect to the axis of chirality) the degree of asym-
metric induction was very sensitive to the solvent. It was thus
clear that THF was the solvent of choice; using CH2Cl2 led to a
considerable decrease in enantioselectivity (Table 1, entries 13,
14, 17 and 15, 16, 18). It is also noteworthy that in a THF med-
ium, complex 4b was the best stereoselector among the catalytic
systems based on ligand 3b.
As
a whole, the data obtained using substrates 7a,b and
CF3CH2OH as the reaction medium are in good agreement with
the well-known positive influence of fluorinated alcohols on
activity and stereoselectivity in Rh-catalyzed asymmetric
hydrogenations.37,38

K. N. Gavrilov et al. / Tetrahedron: Asymmetry 23 (2012) 1052–1057
1055
purchased from Aldrich and Acros Organics and used without
further purification.
3. Conclusion
In conclusion, we have described the successful application of
novel C1-symmetric P,P-bidentate diastereomeric diphosphorami-
dites in Pd-catalyzed asymmetric allylations and in Rh-catalyzed
asymmetric hydrogenations. These ligands have the advantage of
being readily prepared in a few steps from commercial (S)-pyroglu-
tamic acid and (Sa)- or (Ra)-BINOL, low-cost chiral precursors. For
all of the investigated catalytic reactions we found that the abso-
lute configuration of the binaphthyl moieties unequivocally deter-
mines the absolute configuration of the products obtained. In some
cases, the asymmetric induction was very sensitive to the solvent
4.2. General procedure for the preparation of ligands 3a,b
A solution of diamine 1 (0.19 g, 1 mmol) in toluene (7 mL) was
added dropwise to a vigorously stirred solution of the appropriate
enantiomer 2a or 2b (0.7 g, 2 mmol), Et3N (0.7 mL, 5 mmol), and
DMAP (0.024 g, 0.2 mmol) in toluene (10 mL). The mixture was
then heated to boiling point, stirred for 30 min, and then cooled
to 20 °C. The resulting suspension was filtered through a short plug
of aluminum oxide, the column was washed twice with toluene
(8 mL) and the solvent evaporated under reduced pressure
(40 Torr). The product was dried in vacuo (1 Torr, 1 h).
nature. In particular, in the Rh-catalyzed hydrogenations of
a-
dehydrocarboxylic acid esters, the strongly polar CF3CH2OH was
the solvent of choice. A comparison of the results obtained with
the novel diphosphoramidites 3a,b and well-known L1a–d [up to
95% and 80% ee in Rh-catalyzed hydrogenation of (Z)-methyl 2-
acetamido-3-phenylacrylate, respectively]16 and L2a,b [up to 84%
and 75% ee in Pd-catalyzed alkylation of (E)-1,3-diphenylallyl ace-
tate with dimethyl malonate, respectively]20 showed that 3a,b are
comparable or even more efficient stereoselectors. As a result,
additional studies highlighting the potential of these new ligands
in other asymmetric reactions are currently in progress in our
laboratories.
4.2.1. (Sa,Sa)-N-Benzyl-N-(((2S)-1-(dinaphtho[2,1-d:10,20-f][1,3,
2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-
d:10,20-f][1,3,2]dioxaphosphepin-4-amine 3a
White powder (0.68 g, yield 83%). ½a D20
¼ þ168:7 (c 1.0, CHCl3).
ꢁ
1H NMR (CDCl3, 25 °C): d = 1.62–1.75 (m, 4H, CH2CH2), 2.60–2.68
(m, 1H, 2(CH2N)), 2.78–2.92 (m, 3H, 2(CH2N)), 3.86 (dd,
3
2JH,H = 14.7 Hz, JH,P = 8.3 Hz, 1H, CH2, Bn), 4.11–4.19 (m, 1H,
CHN), 4.26 (dd, JH,H = 14.7 Hz, JH,P = 5.4 Hz, 1H, CH2, Bn), 7.21–
7.28 (m, 3H, CH, aryl), 7.36–7.52 (m, 16H, CH, aryl), 7.69 (d,
3JH,H = 9.0 Hz, 1H, CH, aryl), 7.91–8.08 (m, 9H, CH, aryl). 13C{H}
NMR (CDCl3, 25 °C): dC = 24.0 (s, CH2); 29.6 (d, 3J = 3.9 Hz, CH2);
44.8 (d, 2J = 5.5 Hz, CH2N); 49.0 (d, 2J = 9.9 Hz, CH2N); 49.9 (dd,
2J = 27.6 Hz, 3J = 6.0 Hz, CH2N); 55.7 (d, 2J = 28.1 Hz, CHN); 121.8,
121.9 (s, CH, binaphthyl); 122.1 (d, 3J = 1.7 Hz, CH, binaphthyl);
122.3 (s, CH, binaphthyl); 122.5 (d, 3J = 2.2 Hz, C, binaphthyl);
122.6 (d, 3J = 2.2 Hz, C, binaphthyl); 124.1, 124.2 (s, C, binaphthyl);
124.6, 124.7, 124.8, 124.9, 125.4, 126.1 (s, CH, binaphthyl); 126.2
(br s, 2 ꢀ CH, binaphthyl); 126.9 (s, CH, phenyl); 127.1 (br s,
2 ꢀ CH, phenyl); 127.4 (s, CH, binaphthyl); 128.2 (br s, 2 ꢀ CH, phe-
nyl); 128.3 (s, CH, binaphthyl); 128.4 (br s, 3 ꢀ CH, binaphthyl);
129.0 (br s, 2 ꢀ CH, binaphthyl); 129.1, 129.8, 130.2, 130.3, 130.4
(s, CH, binaphthyl); 130.7, 130.8, 131.4, 131.5, 132.6, 132.8,
132.9, 133.0 (s, C, binaphthyl); 137.7 (s, C, phenyl); 149.4 (s, CO,
binaphthyl); 149.8 (d, 2J = 3.3 Hz, CO, binaphthyl); 149.9 (d,
2J = 2.2 Hz, CO, binaphthyl); 150.6 (d, 2J = 4.4 Hz, CO, binaphthyl).
MS (MALDI TOF/TOF), m/z (I, %): = 819 (18) [M+H]+, 505 (100)
[MꢂC20H12O2P+2H]+, 316 (47) [C20H12O2PH]+. Anal. Calcd for
C52H40N2O4P2: C, 76.27; H, 4.92; N, 3.42. Found: C, 76.51; H,
4.87; N, 3.61.
4. Experimental
4.1. General
31P, 13C and 1H NMR spectra were recorded with a Bruker AMX
400 instrument (162.0 MHz for 31P, 100.6 MHz for 13C and
400.13 MHz for 1H). The complete assignment of all of the reso-
nances in the 13C NMR spectra was achieved by the use of DEPT
techniques and published data.35 Chemical shifts (ppm) were given
relative to Me4Si (1H and 13C) and 85% H3PO4 31P NMR). Mass
(
spectra are recorded with a Bruker Daltonics Ultraflex spectrome-
ter (MALDI TOF/TOF). HPLC analyses were performed on an Agilent
1100 and Stayer instruments using ChiralcelÒ columns. GC was
performed on an Agilent 6890 chromatograph with a Lipodex E
column. Optical rotations were measured on a Perkin–Elmer 341
polarimeter. Elemental analyses were performed at the Laboratory
of Microanalysis (Institute of Organoelement Compounds,
Moscow).
All manipulations were carried out under a dry argon atmo-
sphere in flame-dried glassware and in freshly dried and distilled
solvents. For example, toluene and tetrahydrofuran were freshly
distilled from sodium benzophenone ketyl before use; dichloro-
methane was distilled from NaH. Triethylamine was distilled
over KOH and then over a small amount of LiAlH4 before use.
Column chromatography was performed using silica gel MN Kie-
selgel 60 (230–400 mesh) and MN-Aluminum oxide, basic,
Brockmann Activity 1. Enantiomeric phosphorylating reagents—
(Sa)-2-chlorodinaphtho[2,1-d:10,20-f][1,3,2] dioxaphosphepine 2a
and (Ra)-2-chlorodinaphtho[2,1-d:10,20-f][1,3,2] dioxaphosphepine
2b were prepared according to the literature.39 Pd(allyl)Cl]2 and
starting substrate 5 were prepared analogously to the known
procedures.40 Pd-catalyzed allylic substitution: sulfonylation of
substrate 5 with sodium p-toluenesulfinate and alkylation with
dimethyl malonate were performed according to the appropriate
procedures.36 [Rh(cod)2]BF4 and starting substrate 7b were pre-
4.2.2. (Ra,Ra)-N-Benzyl-N-(((2S)-1-(dinaphtho[2,1-d:10,20-f][1,3,
2]dioxaphosphepin-4-yl)pyrrolidin-2-yl)methyl)dinaphtho[2,1-
d:10,20-f][1,3,2]dioxaphosphepin-4-amine 3b
White powder (0.71 g, yield 87%). ½a D20
¼ þ122:3 (c 1.0, CHCl3).
ꢁ
1H NMR (CDCl3, 25 °C): d = 1.36–1.44 (m, 1H, CH2CH2), 1.46–1.56
(m, 2H, CH2CH2), 1.69–1.77 (m, 1H, CH2CH2), 2.63–2.72 (m, 1H,
2
2(CH2N)), 3.03–3.15 (m, 3H, 2(CH2N)), 3.78 (br d, JH,H = 15.0 Hz,
2
1H, CH2, Bn), 3.86–3.94 (m, 1H, CHN), 4.20 (br d, JH,H = 15.0 Hz,
1H, CH2, Bn), 7.14–7.25 (m, 6H, CH, aryl), 7.32–7.45 (m, 10 H, CH,
3
aryl), 7.49 (d, JH,H = 8.9 Hz, 1H, CH, aryl), 7.55–7.66 (m, 3H, CH,
aryl), 7.78–8.03 (m, 9H, CH, aryl). 13C{H} NMR (CDCl3, 25 °C):
dC = 24.7 (s, CH2); 28.8 (d, 3J = 4.0 Hz, CH2); 43.2 (s, CH2N); 48.8
(br s, CH2N); 50.4 (dd, 2J = 32.7 Hz, 3J = 4.1 Hz, CH2N); 56.6 (dd,
2J = 31.4 Hz, 3J = 3.4 Hz, CHN); 121.9, 122.1 (s, CH, binaphthyl);
122.2 (d, 3J = 3.4 Hz, CH, binaphthyl); 122.3 (s, CH, binaphthyl);
122.9, 123.0 (s, C, binaphthyl); 123.8 (d, 3J = 4.7 Hz, C, binaphthyl);
124.1 (d, 3J = 5.4 Hz, C, binaphthyl); 124.4 (br s, 2 ꢀ CH, binaph-
thyl); 124.5, 124.7, 125.7, 125.8, 125.9, 126.0, 126.7, 126.8, 126.9,
127.0, 127.1 (s, CH, binaphthyl); 128.1 (s, CH, phenyl); 128.2 (br
s, 2 ꢀ CH, phenyl); 128.3 (br s, 3 ꢀ CH, binaphthyl); 128.7 (br s,
2 ꢀ CH, phenyl); 129.7, 129.9, 130.0, 130.1, (s, CH, binaphthyl);
pared as published.41,42 Rh-catalyzed hydrogenation of
a-dehy-
drocarboxylic acid esters 7a,b was performed as published.43
(Sa)- and (Ra)-BINOL, DMAP (4-dimethylamino-pyridine), di-
methyl malonate, BSA (N,O-bis(trimethylsilyl) acetamide), so-
dium p-toluenesulfinate and dimethyl itaconate 7a were

1056
K. N. Gavrilov et al. / Tetrahedron: Asymmetry 23 (2012) 1052–1057
130.5, 130.7, 131.1, 131.3, 132.3, 132.4, 132.7, 132.8 (s, C, binaph-
thyl); 137.5 (s, C, phenyl); 149.1 (s, CO, binaphthyl); 149.6 (d,
2J = 1.4 Hz, CO, binaphthyl); 149.9 (d, 2J = 6.1 Hz, CO, binaphthyl);
150.0 (d, 2J = 6.7 Hz, CO, binaphthyl). MS (MALDI TOF/TOF), m/z
(I, %): = 819 (23) [M+H]+, 505 (100) [MꢂC20H12O2P+2H]+, 316 (64)
[C20H12O2PH]+. Anal. Calcd for C52H40N2O4P2: C, 76.27; H, 4.92; N,
3.42. Found: C, 76.40; H, 5.03; N, 3.15.
was dissolved in an appropriate eluent mixture (8 mL) and a sam-
ple was taken for HPLC analysis.
4.4.3. General procedure for the Rh-catalyzed hydrogenation of
a
-dehydrocarboxylic acid esters 7a,b
A solution of [Rh(cod)2]BF4 (0.002 g, 0.005 mmol) and the
appropriate ligand (0.004 g, 0.005 mmol) in the appropriate sol-
vent (8 mL) was stirred for 40 min. Next, the resulting solution
and the prochiral olefin (0.5 mmol) were transferred to the hydro-
genation device (a standard device for hydrogenation under 1 bar
hydrogen pressure) under a hydrogen atmosphere. The reaction
mixture was stirred at 25 °C for 24 h. The conversions of substrates
7a,b were determined by GC simultaneously with the determina-
tion of the ee values of products 8a,b. In some cases, conversions
were also determined by 1H NMR.
4.3. General procedure for the preparation of complexes 4a,b
A
solution of the appropriate ligand 3a or 3b (0.164 g,
0.2 mmol) in CH2Cl2 (3 mL) was added dropwise over 30 min to a
vigorously stirred solution of [Pd(allyl)Cl]2 (0.037 g, 0.1 mmol) in
CH2Cl2 (2 mL). The mixture was stirred for an additional 1 h, fol-
lowed by the dropwise addition of AgBF4 (0.039 g, 0.2 mmol) in
THF (3 mL) over 30 min. The mixture was then stirred for 1 h,
and the precipitated AgCl was filtered off. The filtrate was concen-
trated at reduced pressure to a volume of approximately 0.5 mL,
and then diethyl ether (10 mL) was added. The precipitated solid
was separated by centrifugation, washed twice with diethyl ether
(7 mL) and dried in vacuo (1 Torr, 1 h).
Acknowledgements
We acknowledge the financial support from the Russian Foun-
dation for Basic Research (Grant No. 11-03-00347-a). A.A.S. thanks
the DAAD Foundation for a research fellowship.
4.3.1. [Pd(allyl)(3a)]BF4 4a
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Sand-colored powder (0.192 g, yield 91%). MS (MALDI TOF/TOF),
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